1292579 玖、發明說明： 【發明所屬之技術領域】 本發明係與電子源用膠、電子源及自體發光面板型顯示 裝置有關；而該自體發光面板型顯示裝置係把該電子源在 陰極配線上形成者；而該電子源係利用電子源用膠所形成 者；而該電子源用膠係用於形成電子源者；而該電子源係 以電場施加來釋出電子者。 【先前技術】 就電場發射型之面板顯示裝置（FED)的一種形式而言，已 經有許多自體發光面板型顯示裝置被揭示；而其電子源係 以電場施加來釋放電子者，且係採用奈米碳管（CNT，Ca比如 Nano Tube)或奈米碳纖等無機質碳材料者。譬如，在 SID99Digest之ΡΡ·1134-1137中就刊載有公稱4·5吋之自體發 光面板型顯示裝置的製作例；而該種電子源係把由奈 管（CNT)和銀（Ag)粒子所混煉之電子源用膠（在銀膠中把奈 米碳管混煉後之物）塗佈或印刷在陰極配線等之導電膜= ，接著將之在大氣中加熱（燒製），並使之固定化。 然而，前述把銀混煉後之奈米碳管或奈米碳纖等無機質 碳材料膠，如在大氣中加熱到400。以上，則因銀的觸媒作 用，會使無機質碳材料（以下亦稱為奈米碳管等）氧化，缴、 C〇2(或CO)而大部份消失；如作為顯示裝置之電子源時，: 無法獲得充份之電子釋出特性，且難以構成具有均則 釋出的電子源。又，不限於銀，即使是含有鎳（Ni)等其包 屬之膠的情形，雖有程度差別，但前述傾向仍維持不、=金 83513 1292579 因此，在以含奈米碳管等及金屬之電子源用膠所形成的 電子源方面，在實施顯示裝置之製作上必要的加熱時，必 須以低於該處理之最適溫度的溫度來進行，或必須在非氧 化環境中進行；而前述必要的加熱係指，該當膠之塗佈膜、 印刷膜 < 燒製等；而前述最適溫度係受一般所認為必要 者。然而，在非氧化環境（真空、氮氣、氬氣等之環境）中的 加熱，因受限於包含加熱裝置在内之處理設備的緣故，所 以難以對應面板顯示裝置的大型化需求。此外，在非氧化 環境中之電子源用膠之燒製上，由於氧化性氣體的殘留或 來自處理設備的發生氣體，會使奈米碳管等部份消失，電 子源之電子釋出性能劣化，或成為導致電子釋出不均一的 要因之一。 在揭示利用電子源用膠（CNT-Ag膠）之電子源形成技術的 文獻方面有 J.M. Kim et al·，New Emitter Techniques for Field Emission Displays (SID 01 DIGEST ρρ·304-307);而該電子 源用膠係把奈米碳管等和銀進行混煉而成者。根據該文獻 ’係把上述電子源用膠實施網版印刷，在大氣中以35(rc進 行燒製來形成電子源，接著，把形成電子源的基板、螢光 體及形成陽極之對向基板，在氬氣中以415 °C進行加熱，並 實施封著。 【發明内容】 上述燒製溫度350°C為分解CNT-Ag膠之有機黏合劑成份 的下限；又，雖設定為無法在大氣中進行400°C以上的加熱 ，但仍以更高溫之燒製為佳。此外，因基板之封著溫度以 83513 1292579 415 C左右為下限，所以在氬氣等之非氧化環境中 著。 然而’為了充份確保電子源之膜内的導電性及其膜強度 ，則以用5〇〇。(：以上來進行燒製為佳；而該電子源係以 CNT-Ag膠所形成者。再者，在氬氣等之非氧化環境中進行 加”’、並播去羌全防止奈米碳管等的氧化，而成為導致電 子釋出不均一的原因。 本發月之一個目的在於提供一種電子源用膠，其係即使 以400°C以上進行燒製，亦可降低奈米碳管等之消失者；又 本發明之其他目的在於提供一種電子源，而其係以該電 子源用膠所形成者；此外，本發明的另一個目的在於提供 一種自體發光面板型顯示裝置，其係具有以電子源用膠所 形成之電子源者。 為了達成上述目的，本發明在包含奈米碳管等和金屬的 膠中添加了硼（B);由於添加了硼，因此可抑制奈米碳管等 的氧化，且在燒製等之加熱處理上，可防止電子釋出特性 的劣化及電子釋出均一性能的劣化。 所添加之棚可採用還原性高之硼單體、硼合金、氧化硼 。由於硼單體、硼合金等本身會優先氧化，故可實際發揮 抑制奈米碳管等之氧化的效果；而氧化硼則可包覆奈米碳 管的懸鍵（dangling bond)形成保護層來防止氧化。此外，在 關於利用氧化硼來提升碳材料之耐氧化性方面，在專利 2749175號及「Chemistry and Physics of Carbon，23卷」中 有記載。 83513 -9- 1292579 再者，由於氧化硼在45(TC熔融，故具有可讓奈米碳管等 固著於金屬粒子上的效果；因此，可防止奈米碳管等從電 子源之膜脫落，且可防止使用電子源之面板型顯示裝置在 動作中引發放電；而該電子源之膜係以含有奈米碳管等之 電子源用膠燒製而形成者。相對的，在未對奈米碳管等實 施耐熱處理的情形時，則在顯示裝置之製程的熱處理工序 上，則因奈米碳管等燃燒，或因受到損傷，而導致奈米碳 管等之放電特性大幅度劣化等問題。以下，列舉本發明之 代表性結構。 (1) 在電子源用膠中至少包含金屬或其合金、無機質碳材 料、彌（B)。 (2) 此時，前述硼係以下列型態中之至少一種而被包含： 硼單體、硼與其他金屬之固溶體、硼與其他金屬的金屬間 化合物、或含硼之化合物。 (3) 又，前述硼係以下列型態中之至少一種而被包含：氧 化硼、硼酸、硼之醇鹽。 (4) 或，前述硼係以下列型態中之至少一種而被包含：硼 單體；硼與其他金屬之固溶體；硼與其他金屬之金屬間化 合物；或含硼之化合物；及前述硼係以下列型態中之至少 一種而被包含：氧化硼；硼酸；及硼之醇鹽。 . » (5) 前述金屬間化合物為下列中之至少一種：AgB2、Ni3B 、Ni2B。 (6) 或，前述含硼之化合物係NaBHU。 (7) 前述硼之含有量之對金屬或合金的元素比率（atomic 83513 -10- 1292579 ratio)概略為0.07乃至30’而以0.1乃至15為佳，如為〇 4乃至 15為最理想。 (8) 前述電子源用膠中所含之前述金屬或合金之總量，係 在去掉該當電子源用膠中所含之有機成份及無機質碳材料 後，概略占所剩部份之5〇體積％以上。 (9) 又，前述電子源用膠中所含之前述無機質碳材料的總 量對該當電子源用膠中所含之前述金屬或合金之總量的元 素比率，概略為0·1乃至9。 (10) 前述電子源用膠中所含之前述無機質碳成份係包含 奈米碳管或奈米碳纖中之至少一種。 、 (11) 又，前述奈米碳管或奈米碳纖含有量相對於前述電子 源用膠中所含之前述無機質碳成份的總量，如以重量％計 算’概略在1%以上，而以10%以上為佳。 (12) 前述電子源用膠中所含之前述金屬或合金係至少包 含下列中之一種：銀（Ag)、鎳（犯）、金（Au)、鋁（Α1)、鐵（Fe) 、銅（Cu)、鋅（Zn)、鈀（Pd)、鎢（w)、鉬（M〇)、钽（Ta)、鈦（Ti) 、絡（Cr)、錄（ir)。 (13) 則述電子源用膠中所含之前述金屬或合金係使用Ag 或Ni中至少一種為主成份者。 (14) 把前述電子源用膠塗佈或印刷，以概略4〇〇它以上進 行加熱75至於以450 C以上之溫度加熱更佳，然後使之固 定化，來作為電子源。 (15) 自體發光面板型顯示裝置具有陽極，而該陽極具有陰 極配線、控制電極及螢光體；而該陰極配線上具備電子源。 83513 -11 - 1292579 在上述電子源用膠方面，譬如，在奈米碳管和銀膠 (CNT-Ag膠）中添加硼；因此可抑制奈米碳管等的因氧化 消失。還原性高的硼本身會優先氧化來抑制奈米碳管的氧 化氧化刪可包覆奈米碳管的懸鍵來防止氧化。如此、 ，經由大氣中400°C以上之加熱處理，則奈米碳管不會消失 ’而且可獲得充份之電子釋出特性。 此外，如把硼的添加和在非氧化環境中之加熱合併實施 ，則因氧化性氣體的殘留及發生氣體的容許範圍較大，= 可局部性防止奈米碳管的氧化，且特別可改善電子釋出之 均"4生。 又，由於氧化硼在45(TC熔解，可發揮讓奈米碳管固著於 金屬粒子上的效果；故可防止奈米碳管從形成後之電子源 的膜上脫落，且可避免引發放電。 【實施方式】 以下，參考實施例之圖式，針對本發明之實施型態作詳 細說明。以下，以奈米竣管作為無機質碳材料之例，來進 行說明。把在銀膠中將奈米碳管混練後之物塗佈在基板上 ，接著將之加熱（燒製）’使之固定化，來作為電場發射型之 面板顯示裝置（FED)之電子源，同時，把平均粒徑i乃至⑽ 2銀粒子及奈米碳管（含石墨及無定形碳等）和纖維素系黏 a、分散劑、添加劑等混練，來製作成電子源用膠。 此時，把無機質碳成份（C :奈米好、石墨、無定形碳 等）之量的對銀元素比（C/Ag)調整為18(c/Ag、重量比02) ，來製作Ag.c_。此—情況之奈米碳管的材料，係使用 83513 •12- 1292579 在稀有氣體中以電弧放電法所製作之多層壁CNT。 圖1係以曲線圖來顯TF電流密度之電場依存性的說明圖 ;而該曲線圖係依照如下兩項變化，由座標上的點所連結 而成者：因Ag-CNT膠之加熱條件所引起的電子釋出特性變 化，及因硼之添加所引起的同樣之電子釋出特性變化；而 說明圖之橫軸為電場強度（V/μιη)、縱軸為電流密度 (mA/cm2)。在圖中，白色三角△之曲線圖係把Ag-CNT膠在 大氣中以350 °C燒製的情形；白色圓圈〇之曲線圖係把 Ag-CNT膠在大氣中以450°C燒製的情形；白色四角□之曲 線圖係把Ag_CNT膠在大氣中以590°C燒製的情形；黑色四 角·之曲線圖係把Ag-CNT膠在氮氣環境中以590°C燒製的 情形；白色星號☆之曲線圖係把Ag-B-CNT膠在大氣中以 590°C燒製的情形。 為了獲得該曲線圖，對玻璃基板之表面以3 mm角的區域 實施Ag-CNT膠之厚膜印刷，接著，在大氣中以350°C、 450°C、590°C分別進行30分鐘之燒製，如此則製作出燒製 膜之樣本。在離該樣本燒製膜的前方400 μπι之處，配置陽 極，來進行電子釋出特性的測定。 如白色三角△、白色圓圈〇、白色四角□之各曲線圖所 示’燒製溫度越高，則電子釋出所需之電場越高（電子釋出 越難）；如以590°C進行燒製，則即使是8 V/μιη的高電場也 無法有電子釋出。然而，把同一種膠在氮氣環境中以590°C 所燒製出來者，在約4 V/μιη的電場中可獲得約20 mA/cm2 的電子釋出。 83513 -13- 1292579 在高溫之大氣中進行加熱，則難以充份獲得或完全無法 獲得電子釋出，其可能原因在於：在氧化性環境中加熱， 則奈米碳管等的碳會被氧化成為碳酸氣而燒失之故。但如 僅把所用的奈米碳管以進行加熱，則幾乎不會燒失。 其原因在於：銀發揮了氧化觸媒的作用，而促進了奈米碳 管的氧化。因此，在奈米碳管的膠中如不含Ag(或其他具有 氧化觸媒作用的金屬）的話，則奈米碳管亦可禁得起在大氣 中以400°C進行加熱。 ' 然而，如從確保使用奈米碳管（CNT)之電子源的導電性， 及確保電子源之膜的強度的觀點而言，在奈米碳管的膠中 以含有Ag(Ag粒子或其他金屬粒子）為佳。又，在含有氧化 觸媒作用之金屬的奈米碳管的膠方面，如在氮氣環境（或在 其他非氧化性環境）中進行加熱，則可抑制奈米碳管之氧化 :但如針對公稱40奴大型基板的製程，則不利於實現在 上述非氧化性環境中之燒製處理。1292579 发明, invention description: [Technical Field] The present invention relates to an electron source adhesive, an electron source, and an auto-luminescence panel type display device; and the self-luminous panel display device uses the electron source at a cathode The electron source is formed by an electron source glue; and the electron source is used to form an electron source; and the electron source is applied by an electric field to release electrons. [Prior Art] In terms of a form of a field emission type panel display device (FED), many self-luminous panel type display devices have been disclosed; and an electron source is applied by an electric field to release electrons, and is employed. Inorganic carbon materials such as carbon nanotubes (CNT, Ca such as Nano Tube) or nano carbon fiber. For example, in SID99 Digest ΡΡ 1134-1137, a production example of a self-luminous panel display device having a nominal 4·5 刊 is published; and the electron source is made of a nanotube (CNT) and silver (Ag) particles. The kneaded electron source is coated or printed on a conductive film of a cathode wiring or the like with a glue (a material obtained by kneading a carbon nanotube in a silver paste), and then heated (fired) in the atmosphere, and Fixed. However, the above-mentioned inorganic carbon material such as carbon nanotubes or nano carbon fibers which have been kneaded by silver is heated to 400 in the atmosphere. In the above, due to the catalytic action of silver, the inorganic carbon material (hereinafter also referred to as a carbon nanotube, etc.) is oxidized, and most of C 〇 2 (or CO) is lost; for example, as an electron source of a display device At the time, it is impossible to obtain sufficient electron emission characteristics, and it is difficult to constitute an electron source having a uniform release. Further, it is not limited to silver, and even if it contains a rubber such as nickel (Ni), although the degree is different, the above tendency is maintained. = Gold 83513 1292579 Therefore, a carbon nanotube or the like and a metal are included. The electron source formed by the electron source gel must be heated at a temperature lower than the optimum temperature of the treatment, or must be performed in a non-oxidizing environment, in order to perform the necessary heating for the production of the display device; The heating means a coating film of a glue, a printing film, a firing, etc., and the above-mentioned optimum temperature is generally considered to be necessary. However, heating in a non-oxidizing environment (environment of vacuum, nitrogen, argon, etc.) is limited by the processing equipment including the heating device, so that it is difficult to cope with the demand for enlargement of the panel display device. In addition, in the non-oxidizing environment, the electron source is fired by the glue, and due to the residual of the oxidizing gas or the gas generated from the processing equipment, the carbon nanotubes and the like are partially eliminated, and the electron emission performance of the electron source is deteriorated. Or become one of the factors that cause the non-uniformity of electronic release. JM Kim et al., New Emitter Techniques for Field Emission Displays (SID 01 DIGEST ρρ·304-307); and the electron source is disclosed in the literature for revealing electron source formation technology using electron source glue (CNT-Ag glue); The carbon nanotubes and the like are mixed with silver by a glue system. According to this document, the electron source is screen-printed, and the electron source is formed by firing at 35 (rc) in the atmosphere, and then the substrate, the phosphor, and the anode-forming substrate on which the electron source is formed are formed. The film is heated at 415 ° C in argon gas and sealed. [Invention] The firing temperature of 350 ° C is the lower limit of the organic binder component of the CNT-Ag gel; In the case of heating at 400 ° C or higher, it is preferably fired at a higher temperature. Further, since the sealing temperature of the substrate is about 83,513,1,292,579 415 C as the lower limit, it is in a non-oxidizing environment such as argon. 'In order to fully ensure the conductivity in the film of the electron source and the film strength, it is preferably 5 Å. (: The above is preferably performed by firing; and the electron source is formed by CNT-Ag glue. In addition, in the non-oxidizing environment such as argon gas, the addition of "" and the removal of the ruthenium prevent oxidation of the carbon nanotubes and the like, which causes the electron emission to be uneven. One of the purposes of this month is to provide a Electron source glue, even at 400 ° C The firing is performed, and the disappearance of the carbon nanotubes or the like can also be reduced; and another object of the present invention is to provide an electron source which is formed by the electron source glue; further, another object of the present invention Provided is a self-luminous panel type display device having an electron source formed of a glue for an electron source. In order to achieve the above object, the present invention adds boron (B) to a gel containing a carbon nanotube or the like and a metal. When boron is added, oxidation of a carbon nanotube or the like can be suppressed, and deterioration of electron emission characteristics and deterioration of electron emission uniformity can be prevented in heat treatment such as baking. The boron monomer, the boron alloy, and the boron oxide having high reductivity are used. Since the boron monomer and the boron alloy are preferentially oxidized by themselves, the effect of suppressing the oxidation of the carbon nanotubes or the like can be actually exhibited; and the boron oxide can be coated. The dangling bond of the carbon nanotube forms a protective layer to prevent oxidation. In addition, regarding the use of boron oxide to enhance the oxidation resistance of the carbon material, Patent No. 2749175 and "Chemistry and Physics" In the case of the carbon, the volume of the film is as follows: 83513 -9- 1292579 In addition, since boron oxide is melted at 45 (TC), it has an effect of allowing a carbon nanotube or the like to be fixed to the metal particles; The carbon nanotubes and the like are detached from the film of the electron source, and the panel type display device using the electron source is prevented from causing discharge during the operation; and the film of the electron source is fired with an electron source containing a carbon nanotube or the like. In the case where the heat treatment is not performed on the carbon nanotubes or the like, the heat treatment process of the display device is caused by burning of the carbon nanotubes or the like, or damage due to damage. Problems such as greatly deteriorated discharge characteristics of carbon tubes and the like. Hereinafter, representative structures of the present invention are listed. (1) The metal source adhesive contains at least a metal or an alloy thereof, an inorganic carbon material, and a binder (B). (2) At this time, the boron is contained in at least one of the following types: a boron monomer, a solid solution of boron and another metal, an intermetallic compound of boron and another metal, or a compound containing boron. (3) Further, the boron is contained in at least one of the following types: boron oxide, boric acid, and boron alkoxide. (4) Alternatively, the boron is contained in at least one of the following types: a boron monomer; a solid solution of boron and another metal; an intermetallic compound of boron and another metal; or a boron-containing compound; Boron is included in at least one of the following types: boron oxide; boric acid; and boron alkoxide. (5) The aforementioned intermetallic compound is at least one of the following: AgB2, Ni3B, Ni2B. (6) Alternatively, the boron-containing compound is NaBHU. (7) The element ratio of the boron content to the metal or alloy (atomic 83513 -10- 1292579 ratio) is preferably 0.07 to 30' and preferably 0.1 to 15, and most preferably 〇 4 or 15 is preferable. (8) The total amount of the metal or alloy contained in the gel for the electron source is obtained by removing the organic component and the inorganic carbon material contained in the gel for the electron source, and roughly occupying 5 〇 of the remaining portion %the above. (9) Further, the ratio of the total amount of the inorganic carbon material contained in the gel for electron source to the total amount of the metal or alloy contained in the gel for electron source is preferably from 0.1 to 9. (10) The inorganic carbon component contained in the gel for electron source contains at least one of a carbon nanotube or a carbon fiber. (11) Further, the amount of the carbon nanotube or the carbon fiber content is less than or equal to the total amount of the inorganic carbon component contained in the rubber for the electron source, and is substantially 1% or more. More than 10% is better. (12) The foregoing metal or alloy contained in the gel for electron source includes at least one of the following: silver (Ag), nickel (off), gold (Au), aluminum (Α1), iron (Fe), copper (Cu), zinc (Zn), palladium (Pd), tungsten (w), molybdenum (M〇), tantalum (Ta), titanium (Ti), complex (Cr), and recorded (ir). (13) The above-mentioned metal or alloy contained in the gel for electron source uses at least one of Ag or Ni as a main component. (14) The above-mentioned electron source is coated or printed with a paste, and it is preferably heated 75 to be heated at a temperature of 450 C or more, and then fixed as an electron source. (15) A self-luminous panel type display device has an anode having a cathode wiring, a control electrode, and a phosphor; and the cathode wiring is provided with an electron source. 83513 -11 - 1292579 In the above-mentioned glue for electron source, for example, boron is added to a carbon nanotube and a silver paste (CNT-Ag paste); therefore, oxidation of a carbon nanotube or the like due to oxidation can be suppressed. The highly reductive boron itself is preferentially oxidized to inhibit the oxidation of the carbon nanotubes and the dangling bonds of the carbon nanotubes to prevent oxidation. In this way, the carbon nanotubes do not disappear by heat treatment at 400 ° C or higher in the atmosphere, and sufficient electron emission characteristics can be obtained. In addition, if the addition of boron and the heating in a non-oxidizing environment are combined, the residual range of the oxidizing gas and the allowable range of the generated gas are large, and the oxidation of the carbon nanotubes can be locally prevented, and particularly improved. The electronic release rate is "4 students." Moreover, since boron oxide is melted at 45 (TC), the effect of fixing the carbon nanotubes on the metal particles can be exhibited; therefore, the carbon nanotubes can be prevented from falling off from the film of the formed electron source, and the discharge can be prevented. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings of the embodiments. Hereinafter, an example in which a nanotube is used as an inorganic carbon material will be described. The carbon nanotubes are kneaded and coated on a substrate, and then heated (fired) to be immobilized as an electron source of a field emission type panel display device (FED), and at the same time, the average particle diameter i And (10) 2 silver particles and carbon nanotubes (including graphite and amorphous carbon) and cellulose-based adhesive a, dispersant, additives, etc., to make a glue for electron source. At this time, the inorganic carbon component (C : The ratio of silver to elemental (C/Ag) of the amount of nano-good, graphite, amorphous carbon, etc. is adjusted to 18 (c/Ag, weight ratio of 02) to produce Ag.c_. The material of the pipe is to be arc-discharged in rare gases using 83513 • 12-1292579 Multi-wall CNTs produced by electrical method. Figure 1 is an explanatory diagram showing the electric field dependence of TF current density in a graph; and the graph is connected by points on the coordinates according to the following two changes: The change in the electron emission characteristics caused by the heating conditions of the Ag-CNT glue, and the change in the same electron emission characteristics caused by the addition of boron; and the horizontal axis of the graph is the electric field strength (V/μιη), the vertical axis For current density (mA/cm2), in the figure, the curve of white triangle △ is the case where Ag-CNT glue is fired at 350 °C in the atmosphere; the curve of white circle 〇 is glued to Ag-CNT The case where the atmosphere is fired at 450 ° C; the graph of the white square corner is the case where the Ag_CNT glue is fired at 590 ° C in the atmosphere; the curve of the black square corner is the Ag-CNT glue in a nitrogen atmosphere The case of 590 ° C firing; the curve of white asterisk ☆ is the case where Ag-B-CNT glue is fired at 590 ° C in the atmosphere. In order to obtain the graph, the surface of the glass substrate is at an angle of 3 mm. The area is coated with thick film printing of Ag-CNT glue, and then in the atmosphere at 350 ° C, 450 ° C, 590 ° C respectively After firing for 30 minutes, a sample of the fired film was prepared. The anode was placed at a distance of 400 μm from the front of the fired film of the sample to measure the electron emission characteristics. For example, a white triangle △, a white circle The graphs of 〇 and white squares indicate that 'the higher the firing temperature, the higher the electric field required for electron emission (the more difficult it is to release electrons); if it is fired at 590 °C, even 8 V The high electric field of /μιη cannot be electronically released. However, if the same glue is fired at 590 ° C in a nitrogen atmosphere, an electron of about 20 mA/cm 2 can be obtained in an electric field of about 4 V/μm. Released. 83513 -13- 1292579 When heating in a high-temperature atmosphere, it is difficult to obtain electrons completely or completely, which may be caused by the fact that, in the oxidizing environment, carbon such as carbon nanotubes is oxidized. Carbonated gas burned out. However, if only the carbon nanotubes used are heated, they will hardly burn out. The reason is that silver acts as an oxidizing catalyst and promotes oxidation of the carbon nanotubes. Therefore, if the gel of the carbon nanotubes does not contain Ag (or other metal having an oxidizing catalyst effect), the carbon nanotubes can be prevented from being heated at 400 ° C in the atmosphere. 'However, from the viewpoint of ensuring the conductivity of an electron source using a carbon nanotube (CNT) and ensuring the strength of a film of an electron source, Ag (Ag particles or other) is contained in the gel of the carbon nanotube. Metal particles) are preferred. Further, in the case of a gel of a carbon nanotube containing a metal which functions as an oxidation catalyst, such as heating in a nitrogen atmosphere (or in another non-oxidizing environment), oxidation of the carbon nanotube can be suppressed: but as for the nominal The process of 40 slave large substrates is not conducive to the firing process in the above non-oxidizing environment.
Ag等具有氧化觸媒作用之金屬會促進奈米碳管氧化0 失）的現象，在所有碳材料上均為共通；在多層壁cnt及: 層壁CNT、黑錯、類鑽石碳、無定型碳等方面亦可看到同 樣之氧化促進現I就防止碳氧化的手法而言，在特開平 3-27U84號公報、rChemistry _ m 卷」3章208頁有記載；而其係以8_〇(蝴-氧）來包 之懸键者。 接著，根據以上事實來說明本發明之實施例。 [實施例1] 83513 -14- 1292579 在Ag-CNT膠中添加棚（B)，使B/Ag元素比（atomic ratio) 成為0.8(B/Ag重量比0.08)來製成Ag-B-CNT膠。又，該元素 比（atomic ratio)係原子數的比。在硼添加材料方面係使用 硼單體。把該Ag-B-CNT膠在在大氣中以590°C加熱（燒製） 後，則如圖1之白色星號☆之曲線圖所示，在電場強度約3 V/μιη時具有20 mA/cm2之電子釋出。如前所述，在添加硼 的情況下，即使以大氣中590°C加熱非但可進行電子釋出， 而且，比未添加硼之Ag-CNT膠在氮氣環境中加熱的情形， 還具有更良好的電子釋出特性。 圖2A及圖2B係把Ag-CNT膠和Ag-B-CNT膠，分別在大氣 中590°C燒製之電子源之膜的掃描電子顯微鏡照片。圖2A 為Ag-CNT膠之燒製膜；圖2B為Ag-B-CNT膠之燒製膜。在 圖2A中，奈米碳管消失，而僅有銀粒子殘留。在圖2A中， 蠶繭狀所示者為銀（Ag)粒子。相對的，在圖2B中，在銀粒 子之間存在著未氧化而留下之奈米碳管CNT。在圖2B中， 可見到呈纖維狀之奈米碳管CNT。又，在圖2B中，在蠶繭 狀銀粒子之間存在著將之連接的氧化硼（B2〇3)。 此外，針對Ag-CNT亦實施了與本實驗例相同的實驗，結 果顯示，添加硼可抑制氧化燒失，且即使在大氣中加熱也 可獲得良好之電子釋出特性；而該Ag-CNT係使用以熱CVD 法制作之單層壁CNT及多層壁CNT者。 [實施例2] 圖3係Ag-B-CNT膠之電子釋出必要電場的硼依存性說明 圖。在圖3中，Ag-B-CNT膠係使硼B在B/Ag元素比 83513 -15- 1292579 L5〇(B/Art量比請5乃至5则内變化，來製成膠； ，在硼添加原料方面有硼單體及氧化卵办）兩種情形。把 $子源用膠疋印刷膜在大氣中以5赃加熱（燒製）後，針 Μ $ # 20 mA/em2<電子釋出的電場進行測定；其所獲得 的結果如下： 如為添加硼單體的情形’ B/Agit素比在G.G7乃至30範圍 内時，在8 V/_電場以下即可獲得電子釋出；$在該範圍 卜時則即使在1G ν/μηι電場亦無法發現電子釋出（參考圖3 之實線a)。當硼較少的情形日f，其耐氧化保護效果不足； 2對的’备硼過多#，則因爛過度包覆膜表面，因而降低 电子釋出特性。當使用氧化爛為刪添加原料#，B/Ag元素 比在0·35乃至30的範圍内可獲得電子釋出（參考圖3之虛線 b)。從前述結果可知，至少在前述組成範圍（B/Ag元素比） 内’硼之添加顯現了效果。 而在電場發射型之面板顯示裝置（FED)方面，用於從電子 源把電子引出的驅動電壓雖越低越好，但以15〇¥左右以下 為佳。如為該驅動電壓的話，可使用現有之驅動電路，且 可以低價購得。在此，如使用以印刷成形之奈米碳管為電 子源的情形，用於引出電子之到閘極為止的距離為25 ^①左 右（如小於該距離，則難以精確地形成或配置）。 因此’為了使驅動電壓維持在15〇 V以下，必須在6 ν/μηι(150 V/25 μηι)以下的電場獲得所希望的電流密度。在 必要之電流密度方面，從發光亮度的觀點來看，螢光面電 流密度必須有5〜10 mA/cm2。但由於必須置入閘極電極結構 83513 -16- 1292579 ’因此有效之電子源面積被限制在形成電子源之基板的一 半以下。因此，電子源之電流密度必須有10乃至20 mA/cm2。所以，在使用奈米碳管之電子源的特性方面，以 在6 ν/μηι以下的電場可獲得2〇 mA/cm2左右之電流密度為 佳。而可獲得該特性之組成範圍，在B/Ag元素比方面，如 為添加硼單體的情形，約為〇1乃至15 ;而如為添加氧化硼 的情形，則約為〇·4乃至1 5。 當硼單體比氧化硼更低濃度時，仍具有奈米碳管之氧化 防止效果，其原因在於：硼單體本身會比碳更優先氧化， 來抑制奈米碳管的氧化，進而變為氧化硼吸附於奈米碳管 表面’形成保護層；因此具有雙重之保護效果。 然而，因硼（單體）容易氧化且具有吸濕性，當以硼單體對 該當膠進行添加時，嚴格來說，多少含有氧化硼（i^酸） 的可能性很高，所以在硼添加效果中會產生不均勻現象。 因此，在作為FED用之電子源用途時，為了確實獲得良好 之硼添加效果，在添加硼單體之際，把氧化硼之組成範圍 B/Ag元素比調整為〇·4乃至15較理想。 又，使用與銀之金屬間化合物、氫化鈉硼…沾私）、硼酸 (H3B〇3)、B(OCH3)3等之醇鹽作為硼添加材料時，則具有與 硼或氧化硼相同，或介於兩者中間的電子釋出特性。金屬 間化合物或氫化鈉硼係與硼單體同樣，首先，硼本身备氧 來抑制奈米碳管的氧化，變為氧㈣後㈣成奈:碳 k保護層。喊及醇鹽會因加熱而分解，成為氧化棚， 故具有和以氧化硼進行添加時同樣的作用。 83513 -17. 1292579 圖4係把Ag-B-CNT膠在大氣中以590°C進行二次燒製後 之電子源膜（Ag-B-CNT膜）表面的掃描電子顯微鏡照片。已 經有氧化硼保護之奈米碳管（CNT)，其後即使再度進行大氣 加熱，亦具有保護效果。對Ag-B-CNT膜再度以590。(：進行 大氣中加熱後，在圖4的的掃描電子顯微鏡照片中，可明確 觀察到，奈米碳管在該圖中呈現纖維條紋。此外，並無法 觀察到電子釋出特性之劣化。前述現象不僅在印刷膠之燒 製工序上，在隨後之FED面板製造的熱處理上也顯示了耐 性。具有大幅提升面板製造方面之良率及產品可靠度的可 能性。 [實施例3] 圖5A及圖5B係用於比較Ni-CNT和Ni-B-CNT在大氣中 5 90 °C加熱後之表面的掃描電子顯微鏡照片。圖5A係 Ni_CNT之燒製膜；圖SB係Ni-B-CNT之燒製膜。以與實施例 1同樣的方法製作出Ni-B-CNT膠。鎳（Ni)係使用平均粒徑約 1 μηι者，且把C/Ni元素比調整為ι·2(重量比0.25)、B/Ni元 素比調整為0.45(重量比0.09)。把該Ni-B-CNT膠和不含硼之 Ni-CNT膠在大耽中以590 C進行加熱（燒製）。其結果如圖5B 所π，可發現奈米碳管（CNT)以纖維條紋狀殘留其中；和在 使用銀粒子的膠時一樣，在使用鎳的情形時，硼之添加亦 可防止奈米碳管的氧化。 通常，金屬及其氧化物大多可作為氧化觸媒而發揮作用 ，在混合其他金屬和奈米碳管（或其他之無機質碳成份）的膠 万面，硼具有同樣的效果。經過針對金（Au)、鋁（A1)、鐵（Fe) 83513 -18 - 1292579 、銅（Cu)、鋅（Zn)、鈀（Pd)、鎢（W)、鉬（Mo)、鈕（Ta)、歛（Ti) 、鉻（Cr)、銥（Ir)方面仔細研究，亦確認了具有和銀與鎳約 略同樣的效果。再者’將前述金屬多種混合後，亦可獲得 同樣的效果，此點亦十分明確。 圖6係用於說明本發明之電場發射型之面板顯示裝置之 結構例的要部展開立體圖。在圖中，元件符號1為電子源側 基板；2為電子源配線（陰極配線）；3為Ag-B-CNT之電子源 ;4為金屬栅（控制電極）；5為金屬柵電極之開口部（電子通 過孔）；6為螢光面側基板，其係在内面具備陽極及螢光體 者。在本實施例中係使用實施例1之Ag_B_CNT膠。首先， 把銀膠在電子源側基板1上進行印刷及燒製，來形成電子源 配線2。接著’在其上面印刷作為電子源之Ag-B-CNT膠。 將之在大氣中以5901進行燒製為電子源之後，把具有開口 部5之金屬栅電極4實施重疊配置。 在把金屬柵電極4固定於電子源側基板1之内面時係使用 玻璃料（未在圖中顯示）。為了利用該玻璃料使金屬柵電極4 固著，因此在大氣中以45〇°C實施加熱。而使金屬柵電極4 之開口部5的下端與Ag-B-CNT表面的距離約為25 μηι。 又，圖7係用於說明維持電子源側基板和螢光面侧基板於 特定距離之維持結構之一例的概略立體圖。電子源側基板i 與螢光面側基板6之間係介在著隔板（或間隔物）7，並利用框 玻璃（未在圖中顯示）及玻璃料（未在'圖中顯示）把兩基板之 周邊進行封著；而該電子源側基板1上係形成有上述電子源 配、’泉2电子源3、及金屬拇電極4者。而該封著係在大氣中 83513 -19- 1292579 以430°C進行。其後，以35〇艽持續加熱，進行兩基板間的 排氣，並實施真空封膠。 圖8係在本發明中，用於說明顯示裝置之驅動方式之一例 的等價電路。在該顯示裝置中，朝χ方向並列設置著向y方 白L伸的η條电子源配線（陰極配線）2。又，朝y方向並列設 置著向X方向延伸的m條控制電極（金屬柵）4，與陰極配線2 一起構成m列X η行的矩陣。 在構成該顯示裝置之電子源側基板的周邊配置有掃描電 路60及影像訊號電路50。各控制電極4分別利用控制電極端 子40(Υ1、γ2、"Ym)與掃描電路6〇連接。而各陰極配線2 分別利用陰極端子20(Χ1、Χ2、"·χη)與影像訊號電路5〇連 在主矩陣配置的陰極配線2和控制電極4之交叉部的各像 素上，設置有電子源；而該電子源係在前述實施例中所說 明，以含有硼之奈米碳管膠塗佈燒製所形成之任何一種。 又，在前述實施例中，係以各交叉部之每一個像素有一個 电子源為例進行說明，但其實並不限於此，把二個以上之 電子源配列於一個像素區域中亦可。圖中之R、G、Β分別 為形成彩色之一像素的紅（R)、綠（〇})、藍（B)單色像素；而 從螢光體可放出與各色對應的光。 掃描電路60及影像訊號電路50係被未在圖中顯示的主電 腦施加用於顯示的各種訊號。掃描電路6〇被輸入同步訊號 61。掃描電路60係介以控制電極端子4〇來選擇控制電極4之 矩陣之列，並施加掃描訊號電壓。 83513 -20 - 1292579 另一方面，影像訊號電路50被輸入影像訊號51。影像訊 號電路50係介以陰極端子2〇 (XI、X2、."Xn)與陰極配線2 連接；選擇矩陣之行，並把與影像訊號51對應之電壓施加 到被選擇的陰極配線上。如此一來，在控制電極4和陰極配 線2上被依序選擇之特定之像素會依特定的色光進行發光 ，顯示出二次元之影像。 根據實施例之利用奈米碳管為電子源的顯示裝置，可實 現較低電壓、高效率，且無顯示不均勻現象之明亮FED顯 示裝置。 如上所述，本實施例之Ag-B-CNT膠可在相當高的溫度 (590°C)進行大氣中燒製，因此Ag-B-CNT所形成的電子源3 具有充份的強度與充份的導電性。此外，即使隨後經過熱 處理，奈米碳管並不會氧化（燒失），故可獲得充份的電子釋 出。在該FED顯示裝置方面，針對位於螢光面侧基板6之内 面的陽極施加7 kV，以柵電壓1〇〇 V(60 Hz驅動）使之動作的 結果，獲得了該類顯示裝置的足夠亮度500 cd/m2。 相對的，使用先前之Ag-CNT膠，以與上述同樣的製程製 作出顯示裝置，結果卻幾乎不發光。在Ag-CNT膠方面，為 了抑制奈米碳管的氧化，亦以350°C為該當膠之燒製溫度進 行試燒。在該情況下，也和其他以450°C實施熱處理時一樣 ’會使電子源膜產生劣化，在同一驅動條件時，其亮度僅 獲得使用Ag-B-CNT情形的約一半而已。再者，把所有FED 製造方面的熱處理也試著在可置換氮氣之裝置中進行，但 其亮度卻明顯比使用Ag-B-CNT膠在大氣中進行熱處理的 83513 -21 - 1292579 情形為低。該結果說明了 ：在用於組成FED之熱處理方面 ’無法避開來自各構成材料或製造治具等的發生氣體，難 以維持完全的非氧化環境。 而使用Ag-B-CNT膠為電子源的情形時，把燒製和隨後的 熱處理都在氮氣中進行，則出現了發光均一性更加提升的 現象。其可能原因為：硼所產生的奈米碳管保護效果和非 氧化性環境所產生之保護效果重疊，因此非僅奈米碳管之 宏觀性氧化、燒失等受到抑制，連奈米碳管表面局部的微 觀性氧化也受到抑制。 如上所述，使用本實施例之Ag-B-CNT膠為電子源的情形 ，即使是在大氣中的加熱處理，也可製造出具有充份性能 的FED ;因此，可提供低成本、高品質的顯示裝置。再者 ，如與以氮氣等在非氧化性環境中之加熱處理併用，則可 更提升發光均一性。因此，可實現高精密度、高畫質的顯 示裝置。 而在以芫全非氧化性環境中實施熱處理來作為無添加硼 時之可能代替案的話，由於構成構件會產生發生氣體之故 ，因此實際上相當困難。因此，對以奈米碳管為電子源的 FED技術而T，在使用奈米碳管的電子源中添加硼可謂無 可或缺；而本發明不僅包含添加了硼之電子源用膠，還包 含以之製作的電子源，及具備該電子源之顯示裝置。 此外，在次要功效方面，本發明具有防&FED顯示裝置 之内部放電的效果；其可能的原因為：氧化硼在45〇。〇左右 熔融，目此可使奈米碳管和金屬粒子固著。如此則可抑制 83513 -22- 1292579 因放電而導致的面板破損，提高FED顯示裝置的可靠度。 在本發明之實施例中，係以奈米碳管CNT(多層壁CNT& 單層壁CNT，廣義而言，即奈米碳纖）為電子放射材料進行 說明’但如電子放射材料為無機質碳材料，則具有同樣的 效果。在奈米碳管以外的無機質碳材料方面，譬如，可使 用鑽石、類鑽石碳、黑鉛、無定型碳；如使用其混合物亦 可。但奈米碳管在碳材料中為優秀之電子放射材料，因此 ’在無機質碳成份内以包含1%，乃至於1〇%上為佳。 斤又，在金屬膠中，除了金屬之外，多半含有玻璃等無機 質黏合劑。但在該情況，為了發現充份的導電性，通常會 進行凋整，使金屬占有金屬·無機質黏合劑體積之一半以 上在本發明中，當然也以使金屬成份比無機質黏合劑多 為佳。 此外，在本發明之實施例中，在硼之添加方面，係在製 作好金屬與奈米碳管之混合膠後，再添加棚；但如預先把 奈米碳管、無機質碳成份及進行混合處理後，再加入金 屬成份亦可；或是，同時進行混合亦可。 “ 此外，树明並不受限於上述實施例的結構 並不限於FED，只 可進行種種的變更 要在本發明之技術思想的範 ’適用對象 圍内，當然 如上所述，根據本發明，硼之添加可提升膠的耐熱性； 而孩膠係把奈米礙管進行混煉者。尤其在咖製程 不須要在非氧條環境中進行電子賴製工序、基板封著 序而可使用般的加熱爐（或燒製爐），故有助於降低製 83513 -23 - 1292579 造成本。如併用硼之添加、在非氧化性環境中加熱或燒製 ，則可進一步提升電子釋出之均一性，及提供高品質之顯 示裝置。此外，由於FED對螢光面施加高壓電，如奈米碳 管飛散或附著於特定位置以外的位置，則成為放電之原因 ，可能對顯示裝置造成損傷；但本發明之電子源難以使奈 米碳管飛散，故可降低該危險性，提高可靠度。 【圖式簡單說明】 圖1係以曲線圖來顯示電流密度之電場依存性的說明圖 ;而該曲線圖係依照如下兩項變化，由座標上的點所連結 而成者·因Ag-CNT膠之加熱條件所引起的電子釋出特性變 化，及因硼之添加所引起的同樣之電子釋出特性變化。 圖2A及圖2B係把Ag-CNT膠和Ag_B_CNT膠，分別在大氣 中以590 C燒製之電子源之膜的掃描電子顯微鏡照片。 圖3係Ag-B-CNT膠之電子釋出必要電場的硼依存性說明 圖。 圖4係把Ag-B-CNT膠在大氣中以590〇c進行二次燒製後 之電子源膜（Ag-B_CNT膜）表面的掃描電子顯微鏡照片。 圖5A及圖5B係用於比較Ni_CNT和Ni-B-CNT在大氣中 590 C加熱後之表面的掃描電子顯微鏡照片。 圖6係用於說明本發明之電場發射型之面板顯示裝置之 結構例的要部展開立體圖。 圖7係用於說明維持電子源側基板和螢光面側基板於特 疋距離之維持結構之一例的概略立體圖。 圖8係在本發明中，用於說明顯示裝置之驅動方式之一例 83513 -24· 1292579 的等價電路。 【圖式代表符號說明】 1 電子源側基板 2 陰極配線 3 電子源 4 控制電極 5 開口部 6 勞光面側基板 7 隔板（間隔物） 20 陰極端子 40 控制電極端子 50 影像訊號電路 51 影像訊號 60 掃描電路 61 同步訊號 83513Ag and other metals with oxidizing catalysts promote the oxidation of carbon nanotubes, which are common to all carbon materials; in the multi-wall cnt and: wall CNT, black fault, diamond-like carbon, amorphous In the case of carbon, etc., it is also possible to see that the same oxidation promotion is used to prevent carbon oxidation. It is described in Japanese Unexamined Patent Publication No. 3-27U84, rChemistry _ m, pp. 3, 208; (Fan-Oxygen) to pack the dangling button. Next, an embodiment of the present invention will be described based on the above facts. [Example 1] 83513 - 14 - 1292579 A shed (B) was added to an Ag-CNT paste to make an B/Ag elemental ratio of 0.8 (B/Ag weight ratio of 0.08) to prepare Ag-B-CNT. gum. Further, the ratio of the atomic ratio of the element is the number of atoms. Boron monomers are used in the case of boron-added materials. After heating (firing) the Ag-B-CNT paste at 590 ° C in the atmosphere, as shown in the graph of white star ☆ as shown in Fig. 1, it has 20 mA at an electric field intensity of about 3 V/μηη. The electrons of cm2 are released. As described above, in the case of adding boron, electrons can be released even when heated at 590 ° C in the atmosphere, and it is better than that in the case where the boron-free Ag-CNT paste is heated in a nitrogen atmosphere. Electronic release characteristics. Fig. 2A and Fig. 2B are scanning electron micrographs of a film of an electron source in which Ag-CNT paste and Ag-B-CNT paste were fired at 590 ° C in the atmosphere, respectively. 2A is a fired film of Ag-CNT glue; FIG. 2B is a fired film of Ag-B-CNT glue. In Figure 2A, the carbon nanotubes disappear and only silver particles remain. In Fig. 2A, the silkworm cocoons are shown as silver (Ag) particles. In contrast, in Fig. 2B, there is a carbon nanotube CNT which remains unoxidized between the silver particles. In Fig. 2B, a fibrous carbon nanotube CNT is seen. Further, in Fig. 2B, there is boron oxide (B2〇3) which is connected between the silkworm-like silver particles. Further, the same experiment as in the experimental example was carried out for Ag-CNT, and it was found that the addition of boron suppresses oxidation loss and good electron emission characteristics even when heated in the atmosphere; and the Ag-CNT system Single layer wall CNTs and multilayer wall CNTs produced by thermal CVD are used. [Example 2] Fig. 3 is a diagram showing the dependence of boron on the necessary electric field of electron emission of Ag-B-CNT paste. In Fig. 3, the Ag-B-CNT adhesive system makes boron B in the B/Ag element ratio 83513 -15 - 1292579 L5 〇 (B / Art amount ratio is 5 or 5, to make a glue; There are two cases of adding raw materials, such as boron monomer and oxidized egg. After the $sub source is heated (fired) in the atmosphere with a film of 5 赃, the electric field of the electron is released by the needle Μ $ # 20 mA/em2 < The results obtained are as follows: In the case of monomer, when the B/Agit ratio is in the range of G.G7 or even 30, the electron emission can be obtained below the 8 V/_ electric field; in this range, even in the 1G ν/μηι electric field, The electron emission was found (refer to the solid line a of Fig. 3). When the amount of boron is small, the oxidation protection effect is insufficient; and the two pairs of 'pre-boron excess #, the surface of the film is excessively rotted, thereby lowering the electron emission characteristics. When oxidizing is used as the raw material #, the B/Ag element ratio can be obtained in the range of 0·35 or even 30 (refer to the broken line b of Fig. 3). From the above results, it was found that the addition of boron exhibited an effect at least in the above composition range (B/Ag element ratio). On the other hand, in the electric field emission type panel display device (FED), the driving voltage for drawing electrons from the electron source is preferably as low as possible, but it is preferably about 15 Å or less. If the driving voltage is used, an existing driving circuit can be used and can be purchased at a low price. Here, in the case where a carbon nanotube produced by printing is used as an electron source, the distance for extracting electrons to the gate is about 25 Ω (if it is smaller than this distance, it is difficult to accurately form or arrange). Therefore, in order to maintain the driving voltage below 15 〇 V, it is necessary to obtain a desired current density at an electric field of 6 ν/μηι (150 V/25 μηι) or less. In terms of the necessary current density, the fluorescent surface current density must be 5 to 10 mA/cm2 from the viewpoint of luminance. However, since the gate electrode structure 83513 - 16 - 1292579 ' must be placed, the effective electron source area is limited to less than half of the substrate from which the electron source is formed. Therefore, the current density of the electron source must be 10 or 20 mA/cm2. Therefore, in terms of the characteristics of the electron source using the carbon nanotube, it is preferable to obtain a current density of about 2 mA/cm2 at an electric field of 6 ν/μηι or less. The composition range in which the characteristic can be obtained is about 〇1 or 15 in terms of the B/Ag element ratio, for example, in the case of adding boron monomer, and about 〇·4 or even 1 in the case of adding boron oxide. 5. When the boron monomer has a lower concentration than the boron oxide, it still has the oxidation preventing effect of the carbon nanotubes, because the boron monomer itself is preferentially oxidized more than carbon to suppress the oxidation of the carbon nanotubes and then become The boron oxide adsorbs on the surface of the carbon nanotube to form a protective layer; therefore, it has a double protective effect. However, since boron (monomer) is easily oxidized and hygroscopic, when boron is added as a monomer, strictly speaking, the possibility of containing boron oxide (i^ acid) is high, so boron is present. Unevenness can occur in the added effect. Therefore, in the case of use as an electron source for FED, in order to obtain a favorable boron addition effect, it is preferable to adjust the B/Ag element ratio of the composition range of boron oxide to 〇·4 or 15 when boron monomer is added. Further, when an alkoxide such as an intermetallic compound of silver, sodium hydride with sodium hydride, boric acid (H3B〇3) or B(OCH3)3 is used as the boron-added material, it is the same as boron or boron oxide, or The electron emission characteristics between the two. The intermetallic compound or sodium hydride boron is the same as the boron monomer. First, boron itself is oxygenated to suppress oxidation of the carbon nanotubes, and becomes oxygen (four) and then (four) into a carbon: protective layer. Shouting and alkoxide are decomposed by heating and become an oxidation shed, so they have the same effect as when added with boron oxide. 83513 -17. 1292579 Fig. 4 is a scanning electron micrograph of the surface of an electron source film (Ag-B-CNT film) after the Ag-B-CNT paste was secondarily fired at 590 ° C in the atmosphere. The carbon nanotubes (CNTs) which have been protected by boron oxide have a protective effect even after being heated again by the atmosphere. The Ag-B-CNT film was again at 590. (After heating in the atmosphere, it was clearly observed in the scanning electron micrograph of Fig. 4 that the carbon nanotubes exhibited fiber streaks in the figure. Further, deterioration of the electron emission characteristics was not observed. The phenomenon not only shows resistance in the heat treatment of the subsequent FED panel production in the firing process of the printing paste, but also has the possibility of greatly improving the yield of the panel manufacturing and the reliability of the product. [Embodiment 3] FIG. 5A and Fig. 5B is a scanning electron micrograph for comparing the surface of Ni-CNT and Ni-B-CNT heated in the atmosphere at 5 90 ° C. Figure 5A is a sintered film of Ni_CNT; Figure SB is a Ni-B-CNT The film was fired. Ni-B-CNT paste was produced in the same manner as in Example 1. The nickel (Ni) system was used with an average particle diameter of about 1 μηι, and the C/Ni element ratio was adjusted to ι·2 (weight ratio). 0.25), the B/Ni element ratio was adjusted to 0.45 (weight ratio 0.09). The Ni-B-CNT paste and the boron-free Ni-CNT paste were heated (fired) at 590 C in a large crucible. As shown in Fig. 5B, it can be found that the carbon nanotubes (CNTs) remain in the form of fiber streaks; and when the glue of silver particles is used, In the case of using nickel, the addition of boron also prevents oxidation of the carbon nanotubes. Usually, metals and their oxides mostly function as oxidation catalysts, mixing other metals and carbon nanotubes (or other Boron has the same effect as the inorganic carbon component. It is applied to gold (Au), aluminum (A1), iron (Fe) 83513 -18 - 1292579, copper (Cu), zinc (Zn), palladium ( Pd), tungsten (W), molybdenum (Mo), button (Ta), convergent (Ti), chromium (Cr), and iridium (Ir) have been carefully studied, and it has been confirmed that it has approximately the same effect as silver and nickel. Fig. 6 is a perspective view showing an essential part of a configuration example of a field emission type panel display device according to the present invention, in which a plurality of the above-mentioned metals are mixed, and the same effect can be obtained. , the symbol 1 is an electron source side substrate; 2 is an electron source wiring (cathode wiring); 3 is an electron source of Ag-B-CNT; 4 is a metal gate (control electrode); 5 is an opening portion of a metal gate electrode (electron Through hole); 6 is a fluorescent surface side substrate, which is provided with an anode and a phosphor on the inner surface In the present embodiment, the Ag_B_CNT paste of Example 1 is used. First, silver paste is printed and fired on the electron source side substrate 1 to form an electron source wiring 2. Then, 'printing thereon as an electron source is used. The Ag-B-CNT paste is fired in the atmosphere at 5901 as an electron source, and then the metal gate electrode 4 having the opening 5 is placed in an overlapping manner. The metal gate electrode 4 is fixed to the electron source side substrate 1 A glass frit (not shown) is used for the inner surface. In order to fix the metal gate electrode 4 by the glass frit, heating is performed at 45 ° C in the atmosphere. On the other hand, the distance between the lower end of the opening portion 5 of the metal gate electrode 4 and the surface of the Ag-B-CNT is about 25 μm. In addition, FIG. 7 is a schematic perspective view for explaining an example of a structure for maintaining the electron source side substrate and the phosphor side substrate at a specific distance. The electron source side substrate i and the phosphor side substrate 6 are interposed between the spacers (or spacers) 7, and are made of frame glass (not shown) and frit (not shown in the figure). The periphery of the substrate is sealed; and the electron source side substrate 1 is formed with the electron source, the 'spring 2 electron source 3', and the metal thumb electrode 4. The seal is carried out in the atmosphere at 83513 -19- 1292579 at 430 °C. Thereafter, the film was continuously heated at 35 Torr to evacuate between the substrates, and vacuum sealing was performed. Fig. 8 is an equivalent circuit for explaining an example of a driving method of a display device in the present invention. In the display device, n electron source wirings (cathode wirings) 2 extending in the y direction L are arranged side by side in the χ direction. Further, m control electrodes (metal gates) 4 extending in the X direction are arranged side by side in the y direction, and together with the cathode wiring 2, a matrix of m columns X η rows is formed. A scanning circuit 60 and a video signal circuit 50 are disposed around the electron source side substrate constituting the display device. Each of the control electrodes 4 is connected to the scanning circuit 6A by a control electrode terminal 40 (Υ1, γ2, "Ym). Each of the cathode wirings 2 is connected to each pixel of the intersection of the cathode wiring 2 and the control electrode 4 disposed in the main matrix by the cathode terminal 20 (Χ1, Χ2, "·χη), and is provided with electrons. The source is the same as that described in the foregoing embodiment, and is formed by coating the boron-containing carbon nanotube paste. Further, in the above embodiment, an electron source is provided for each pixel of each intersection as an example. However, the present invention is not limited thereto, and two or more electron sources may be arranged in one pixel region. In the figure, R, G, and Β are respectively red (R), green (〇), and blue (B) monochrome pixels forming one pixel of color; and light corresponding to each color can be emitted from the phosphor. The scanning circuit 60 and the video signal circuit 50 apply various signals for display by the main computer not shown in the figure. The sync circuit 61 is input to the sync signal 61. The scanning circuit 60 selects a matrix of the control electrodes 4 via the control electrode terminals 4, and applies a scanning signal voltage. 83513 -20 - 1292579 On the other hand, the video signal circuit 50 is input with the video signal 51. The video signal circuit 50 is connected to the cathode wiring 2 via a cathode terminal 2 (XI, X2, . "Xn); a matrix is selected and a voltage corresponding to the image signal 51 is applied to the selected cathode wiring. As a result, the specific pixels sequentially selected on the control electrode 4 and the cathode wiring 2 emit light in accordance with a specific color light, and an image of the second element is displayed. According to the display device using the carbon nanotube as an electron source according to the embodiment, a bright FED display device which realizes lower voltage, high efficiency, and no display unevenness can be realized. As described above, the Ag-B-CNT paste of the present embodiment can be fired in the atmosphere at a relatively high temperature (590 ° C), so that the electron source 3 formed by the Ag-B-CNT has sufficient strength and charge. The conductivity of the parts. Further, even if it is subsequently subjected to heat treatment, the carbon nanotubes are not oxidized (burned out), so that sufficient electron emission can be obtained. In the FED display device, 7 kV is applied to the anode located on the inner surface of the phosphor-side substrate 6, and the gate voltage is 1 〇〇V (60 Hz drive), and sufficient brightness of the display device is obtained. 500 cd/m2. In contrast, the display device was fabricated in the same manner as described above using the conventional Ag-CNT paste, and as a result, it hardly emitted light. In the case of the Ag-CNT paste, in order to suppress the oxidation of the carbon nanotubes, the firing temperature of the rubber was also tested at 350 °C. In this case as well, the electron source film was deteriorated as in the case of performing heat treatment at 450 ° C, and the luminance was only about half of that in the case of using Ag-B-CNT under the same driving condition. Furthermore, all heat treatments for FED fabrication were also tried in a nitrogen-replaceable apparatus, but the brightness was significantly lower than in the case of 83513-21- 1292579, which was heat-treated in the atmosphere using Ag-B-CNT glue. This result demonstrates that it is difficult to maintain a complete non-oxidizing environment in the heat treatment for constituting the FED, since it is impossible to avoid the generated gas from each constituent material or manufacturing jig. In the case where Ag-B-CNT paste is used as the electron source, both the firing and the subsequent heat treatment are carried out under nitrogen, and the uniformity of luminescence is further enhanced. The possible reason is that the protective effect of the carbon nanotubes produced by boron overlaps with the protective effect produced by the non-oxidizing environment, so that the macroscopic oxidation and loss of burning of the carbon nanotubes are inhibited, and the carbon nanotubes are inhibited. The local microscopic oxidation of the surface is also suppressed. As described above, in the case where the Ag-B-CNT paste of the present embodiment is used as an electron source, even in the heat treatment in the atmosphere, an FED having sufficient performance can be produced; therefore, low cost and high quality can be provided. Display device. Further, if it is used in combination with heat treatment in a non-oxidizing atmosphere such as nitrogen gas, the uniformity of luminescence can be further improved. Therefore, a high-precision, high-quality display device can be realized. However, when heat treatment is performed in a non-oxidizing environment as a possible alternative to the case where boron is not added, it is actually quite difficult because the constituent members generate gas. Therefore, for the FED technology using a carbon nanotube as an electron source, it is indispensable to add boron to an electron source using a carbon nanotube; and the present invention not only includes an electron source gel to which boron is added, but also The electronic source produced by the electronic source and the display device having the electronic source are included. Further, in terms of secondary efficacy, the present invention has an effect of preventing internal discharge of the & FED display device; the possible cause is that boron oxide is at 45 Å. Melting around the crucible, the carbon nanotubes and the metal particles can be fixed. In this way, the panel damage caused by the discharge of 83513 -22- 1292579 can be suppressed, and the reliability of the FED display device can be improved. In the embodiment of the present invention, a carbon nanotube CNT (multilayer wall CNT & single layer wall CNT, broadly speaking, nano carbon fiber) is described as an electron emitting material, but the electron emitting material is an inorganic carbon material. , it has the same effect. In the case of inorganic carbon materials other than carbon nanotubes, for example, diamonds, diamond-like carbon, black lead, and amorphous carbon can be used; if a mixture thereof is used. However, the carbon nanotubes are excellent electron-emitting materials in carbon materials, so it is preferable to include 1% or even 1% in the inorganic carbon component. In addition, in the metal glue, in addition to metal, most of the inorganic binders such as glass are contained. However, in this case, in order to find sufficient conductivity, it is usually carried out so that the metal occupies one or more of the metal/inorganic binder volume in the present invention, and of course, the metal component is more preferable than the inorganic binder. In addition, in the embodiment of the present invention, in the addition of boron, after the mixture of the metal and the carbon nanotube is prepared, the shed is added; however, if the carbon nanotubes and the inorganic carbon components are mixed and mixed in advance, After the treatment, the metal component may be added; or, the mixture may be mixed at the same time. In addition, the structure of the above-described embodiment is not limited to the FED, and various changes can be made within the scope of the application of the technical idea of the present invention. Of course, as described above, according to the present invention, The addition of boron can improve the heat resistance of the rubber; while the rubber is used to mix the nano tube, especially in the coffee process, it is not necessary to carry out the electronic deposition process in the non-oxygen strip environment, and the substrate can be used in the order of sealing. The heating furnace (or firing furnace) helps to reduce the production of 83513 -23 - 1292579. If the addition of boron is used in a non-oxidizing environment, it can further improve the uniformity of electron emission. And provide a high-quality display device. In addition, since the FED applies high-voltage electricity to the fluorescent surface, such as a carbon nanotube scattering or attaching to a position other than a specific position, it becomes a cause of discharge and may cause damage to the display device. However, the electron source of the present invention is difficult to disperse the carbon nanotubes, thereby reducing the risk and improving the reliability. [Simplified Schematic] FIG. 1 is a graph showing the electric field dependence of current density. The graph is based on the following two changes, the points on the coordinates are connected, the electron emission characteristics caused by the heating conditions of Ag-CNT glue, and the addition of boron The same electron emission characteristics change. Fig. 2A and Fig. 2B are scanning electron micrographs of a film of an electron source in which Ag-CNT glue and Ag_B_CNT glue are respectively fired at 590 C in the atmosphere. Fig. 3 is Ag-B- Figure 4 shows the surface dependence of the electron source film (Ag-B_CNT film) after the secondary firing of the Ag-B-CNT paste in the atmosphere at 590 ° C. Scanning electron micrographs. Fig. 5A and Fig. 5B are scanning electron micrographs for comparing the surface of Ni_CNT and Ni-B-CNT heated in the atmosphere at 590 C. Fig. 6 is a view showing a field emission type panel of the present invention. Fig. 7 is a schematic perspective view showing an example of a structure for maintaining a characteristic distance between an electron source side substrate and a phosphor side substrate. Fig. 8 is a perspective view of the present invention. An example of how the driving device of the display device is driven 83513 Equivalent circuit of -24· 1292579. [Description of symbolic representation of the figure] 1 Electron source side substrate 2 Cathode wiring 3 Electron source 4 Control electrode 5 Opening part 6 Laminate side substrate 7 Separator (spacer) 20 Cathode terminal 40 Control electrode terminal 50 image signal circuit 51 image signal 60 scanning circuit 61 synchronization signal 83513